Poly(hydroxystyrene) stain resist

ABSTRACT

A composition for use as a stain blocker and a method of treating substrates therewith, said composition comprising a polymer of Formula 1 having the following repeating units in random sequence  
                 
wherein 
         R 1  is H, methyl or ethyl;    R 2  and R 3  are each independently H, C 1  to about C 10  alkyl, —COOR 4 , CONR 5 R 6 , or —CN;    R 4  is M, C 1  to about C 20  alkyl, or C 6  to C 10  aryl;    R 5  and R 6  are each independently H, C 1  to C 10  alkyl, C 6  to C 10  aryl, or R 5  and R 6  together with the nitrogen atom form a morpholine, pyrrolidine, or piperidine ring;    R 7  is a C 4  to C 8  alkyl group; M is H, an alkali metal or alkali earth metal; h is about 10 to 100 mole %; i is 0 to about 80 mole %; j is 0 to about 60 mole %; k and n are each independently 0 to about 40 mole %; and m is 0.01 to about 0.5; provided that h+i+j+k+n equals 100, and provided that i+j+k+n is greater than zero, except when h is 100%.

BACKGROUND OF THE INVENTION

The properties of many commercial stain blockers are frequently notretained during washing of the substrate treated with said stainblocker, suffer from light fastness limitations, and have marginalresistance to coffee and mustard stains. Many commercial products whenblended with phenol-formaldehyde resins provide better stain blockingand durability, but still provide only limited UV stability (lightfastness) and have limited coffee and mustard stain resistance.

Allen, in U.S. Pat. No. 5,574,106, discloses polymers wherein a strongacid-containing monomer, a weak acid-containing monomer, and a neutralaromatic-containing monomer are polymerized. More specifically, Allendescribes stain resist compositions formed from (a) from about 8% toabout 40% of a styrene, substituted styrene or phenolic monomer free ofcarboxylic acid groups and strong acid groups, (b) from about 9% toabout 20% of an ethylenically unsaturated strong acid monomer having apKa below 2, and (c) from about 10% to about 62% of an ethylenicallyunsaturated weak acid monomer having a pKa of 3-11, with the weightpercentages described in a ternary diagram. In addition, Allen discloses(a) a preferred system in which the polymers are mixed with sulfonatedphenolic condensates, and (b) that the aromatic neutral monomer must befree of acidic groups. Allen does not describe the use of phenols thathave weakly acidic groups, nor the use of a preformed co-polymer that issulfonated.

It is desirable to have stain blockers having improved performance. Inparticular, improved stain resistance to coffee and mustard stains isdesirable while maintaining UV fastness and durability of theproperties. The present invention provides such a stain blockercomposition, method for its use, and substrates treated therewith.

SUMMARY OF THE INVENTION

The present invention comprises a composition comprising a polymerhaving the following repeating units, said units occurring in anysequence

wherein

R¹ is H, methyl or ethyl;

R² and R³ are each independently H, C₁ to about C₁₀ alkyl, —COOR⁴,CONR⁵R⁶, or —CN;

R⁴ is M, C₁ to about C₂₀ alkyl, or C₆ to C₁₀ aryl;

R⁵ and R⁶ are each independently H, C₁ to C₁₀ alkyl, C₆ to C₁₀ aryl, orR⁵ and R⁶ together with the nitrogen atom form a morpholine,pyrrolidine, or piperidine ring;

R⁷ is a C₄ to C₈ alkyl group;

M is H, an alkali metal or alkali earth metal;

h is about 10 to 100 mole %;

i is 0 to about 80 mole %;

j is 0 to about 60 mole %;

k and n are each independently 0 to about 40 mole %; and

m is 0.01 to about 0.5;

provided that h+i+j+k+n equals 100, and

provided that i+j+k+n is greater than zero, except when h is 100%.

The present invention further comprises a method of providing resistanceto stains in substrates comprising contacting the substrate with apolymer of Formula 1A having the following repeating units, said unitsin any sequence

wherein

R¹ is H, methyl or ethyl;

R² and R³ are each independently H, C₁ to about C₁₀ alkyl, —COOR⁴,CONR⁵R⁶, or —CN;

R⁴ is M, C₁ to about C₂₀ alkyl, or C₆ to C₁₀ aryl;

R⁵ and R⁶ are each independently H, C₁ to C₁₀ alkyl, C₆ to C₁₀ aryl, orR⁵ and R⁶ together with the nitrogen atom form a morpholine,pyrrolidine, or piperidine ring;

R⁷ is a C₄ to C₈ alkyl group;

M is H, an alkali metal or alkaline earth metal;

h is about 10 to 100 mole %;

i is 0 to about 80 mole %;

j is 0 to about 60 mole %;

k and n are each independently 0 to about 40 mole %; and

p is 0 to about 0.5;

provided that h+i+j+k+n equals 100, and

provided that i+j+k+n is greater than zero, except when h is 100%.

The present invention further comprises a substrate treated with apolymer of Formula 1A as described above.

The present invention further comprises a composition comprising apolymer of Formula 2 having the following repeating units, said unitsoccurring in any sequence

wherein

R¹ is H, methyl or ethyl;

R² and R³ are each independently H, C₁ to about C₁₀ alkyl, —COOR⁴,CONR⁵R⁶, or—CN;

R⁴ is H, C₁ to about C₂₀ alkyl, or C₆ to C₁₀ aryl;

R⁵ and R⁶ are each independently H, C₁ to C₁₀ alkyl, C₆ to C₁₀ aryl, orR⁵ and R⁶ together with the nitrogen atom form a morpholine,pyrrolidine, or piperidine ring;

R⁷ is a C₄ to C₈ alkyl group;

R⁸ is H, C₁ to about C₂₀ alkyl, or C₆ to C₁₀ aryl;

R⁹ is H, R¹⁰, or C(O)R¹¹;

R¹⁰ is C₁ to about C₄ alkyl;

R¹¹ is C₁ to about C₄ alkyl, or C₆ to C₁₀ aryl;

h is about 10 to 100 mole %;

i is 0 to about 80 mole %;

j is 0 to about 60 mole %;

k and n are each independently 0 to about 40 mole %; and

m is 0.01 to about 0.5;

provided that h+i+j+k+n equals 100, and

provided that i+j+k+n is greater than zero, except when h is 100%.

DETAILED DESCRIPTION

Herein trademarks are shown in upper case. As used herein, the term“(alkyl)acrylic” indicates acrylic or alkylacrylic, and the term“(alkyl)acrylate” indicates acrylate or alkylacrylate.

The first embodiment of the present invention comprises polymers ofFormula 1 having the following repeating units occurring in anysequence.

wherein

R¹ is H, methyl or ethyl and preferably H or methyl;

R² and R³ are each independently H, C₁ to about C₁₀ alkyl, —COOR⁴,CONR⁵R⁶, or —CN;

R⁴ is M, C₁ to about C₂₀ alkyl, or C₆ to C₁₀ aryl;

R⁵ and R⁶ are each independently H, C₁ to C₁₀ alkyl, C₆ to C₁₀ aryl, or

R⁵ and R⁶ together with the nitrogen atom form a morpholine,pyrrolidine, or piperidine ring;

R⁷ is a C₄ to C₈ alkyl group;

M is H, an alkali metal or an alkaline earth metal, and preferably Na orK;

h is about 10 to 100 mole % and preferably about 40 to about 70 mole %;

i is 0 to about 80 mole % and preferably about 30 to about 60 mole %;

j is 0 to about 60 mole % and preferably about 30 to about 60 mole %;

k and n are each independently 0 to about 40 mole % and preferably about0 to about 10 mole %;

m, also denoted herein as the degree of sulfonation, is from about 0.01to about 0.5, and preferably from about 0.01 to about 0.4 sulfonic acidgroups per hydroxystyrene monomer residue; and

h+i+j+k+n equals 100, and

i+j+k+n is greater than zero, except when h is 100%.

The sulfonated homopolymer of hydroxystyrene is represented by Formula 1in which i, j, k, and n are zero. The sulfonation of the hydroxystyreneis random throughout the polymer.

Preferred polymers of the structure of Formula 1 are a) polymers havingj =k=n=0 and the ratio of h:i from about 50:50 to about 70:30, andpreferably about 60:40, or b) polymers having i=k=n=0 and the ratio ofh:j from about 50:50 to about 70:30, and preferably about 60:40.

The polymers of the present invention are useful to provide stainresistance to substrates. In particular, improved resistance to stainingby coffee and mustard is provided to substrates treated with thepolymers of the present invention.

Polymers of the structure of Formula 1 are formed by polymerization of(a) hydroxystyrene, t-butoxystyrene, acetoxystyrene, alkoxystyrene, orother protected hydroxystyrenes, and (b) one or more monomers of i)monomers of the structure of Formula 3 (see below), ii) maleicanhydride, iii) styrene, and iv) a terminally unsaturated alkene.

The monomer of Formula 3 is an (alkyl)acrylic acid or an (alkyl)acrylateester having the following formula:R ² R ³ C=C(R ¹)—COOR⁸  Formula 3wherein

R¹ is H, methyl or ethyl, and preferably H or methyl;

R² and R³ are each independently H, C₁ to about C₁₀ alkyl, —COOR⁴,CONR⁵R⁶, or —CN, and preferably R² is H and R³ is —COOR⁴;

R⁵ and R⁶ are each independently H, C₁ to C₁₀ alkyl, C₆ to C₁₀ aryl, orR⁵ and R⁶ together with the nitrogen atom form a morpholine,pyrrolidine, or piperidine ring, and preferably R⁵ and R⁶ areindependently H or methyl, and

R⁸ is H, C₁ to about C₂₀ alkyl, or C₆ to C₁₀ aryl, and preferably H ormethyl.

Examples of Formula 3 are (alkyl)acrylic acids, such as (meth)acrylicacids, and their esters, such as methyl and t-butyl (meth)acrylates. Thefree acids are preferred for emulsion polymerization, and the esters forsolution polymerization. When the esters are used, the alkyl group R⁸ isremoved during subsequent hydrolysis steps.

The preparation of the polymers of Formula 1 is by use of polymerizationprocedures known to those skilled in the art. Polymerizations and theremoval of protective groups are discussed in Sheehan et al. in USPatent 2002156199, Watanabe et al. in U.S. Pat. No. 5,412,050, and Linet al., in “Sequence Distribution and Polydispersity Index affect theHydrogen-Bonding Strength of Poly(vinylphenol-co-methyl methacrylate)Copolymers”, Macromolecules, 2005, 38, 6435-6444, each hereinincorporated by reference. Emulsion and solution polymerizationprocedures are well know to those skilled in the art, for instance Ruppet al. discuss suitable emulsion polymerization procedures in U.S. Pat.No. 4,822,862, and Gupta discusses suitable solution polymerizationprocedures in U.S. Pat. No. 4,775,730, each herein incorporated byreference.

The procedures for making polymers of the structure of Formula 1 whereini, k, and n, are zero are know to those skilled in the art, for instancesee “Preparation and Structural Characterization ofPoly(4-vinylphenylacetate-co-maleic anhydride”, J. A. Jones and R. M.Ottenbrite, J. Polym. Chem, Part A: Polymer Chemistry, Vol. 24,1487-95(1986), herein incorporated by reference. In the practice of thepresent invention, any hydroxystyrene, t-butoxystyrene, acetoxystyrene,alkoxystyrene, or other protected hydroxystyrene isomer or mixturethereof may be used, the para isomers are preferred. Several factors areinvolved with the choice of t-butoxystyrene, acetoxystyrene, orhydroxystyrene as the monomer introducing the hydroxystyrene moiety intothe polymer. Hydroxystyrene is relatively unstable and can be the sourceof undesirable impurities. Polymers made with hydroxystyrene may bediscolored or require the use of special solvents.

The polymerization yields an intermediate polymer having the structureof Formula 2 below.

wherein

R¹ is H, methyl or ethyl;

R² and R³ are each independently H, C₁ to about C₁₀ alkyl, —COOR⁴,CONR⁵R⁶, or —CN;

R⁴ is H, C₁ to about C₂₀ alkyl, or C₆ to C₁₀ aryl;

R⁵ and R⁶ are each independently H, C₁ to C₁₀ alkyl, C₆ to C₁₀ aryl, orR⁵ and R⁶ together with the nitrogen atom form a morpholine,pyrrolidine, or piperidine ring;

R⁷ is a C₄ to C₈ alkyl group;

R⁸ is H, C₁ to about C₂₀ alkyl, or C₆ to C₁₀ aryl;

R⁹ is H, R¹⁰, or C(O)R¹¹;

R¹⁰ is C₁ to about C₄ alkyl;

R¹¹ is C₁ to about C₄ alkyl, or C₆ to C₁₀ aryl;

h is about 10 to 100 mole %;

i is 0 to about 80 mole %;

j is 0 to about 60 mole %;

k and n are each independently 0 to about 40 mole %; and

m is 0.01 to about 0.5;

provided that h+i+j+k+n equals 100, and

provided that i+j+k+n is greater than zero, except when h is 100%.

These intermediate polymers of Formula 2 comprise a further embodimentof the present invention, and are useful in making the polymers ofFormula 1. Hydrolysis of the polymer of Formula 2 yields the polymer ofFormula 1.

Any alkoxy groups, for instance acetoxy groups, if present, are removedby hydrolysis or preferably by base-mediated transesterification asdescribed by Sheehan et al, in U.S. Pat. No. 6,759,483. If present, theester group C(O)OR⁴ is removed by suitable hydrolysis based on the typeof ester group, for example the t-butyl group is removed by acidhydrolysis effected by well known reagents such as HCl ortrifluoroacetic acid. If present, the cyclic anhydride ring is opened bybase hydrolysis. The hydroxystyrene monomer residues are optionallysulfonated.

The alkoxy groups are to be removed after polymerization whether or notthe polymer is subsequently sulfonated. All protecting groups impedesulfonation. Examples of alkoxy groups include, but are not limited to,t-butoxy, acetoxy, and methoxymethyl (—CH_(2OCH) ₃). The t-butoxy andmethoxymethyl groups are easily removed by acid hydrolysis, while theacetoxy group is readily removed by base hydrolysis ortransesterification. Although the acetoxy group is less easy to remove,requiring base hydrolysis, the monomer is less expensive and morereadily available. When present, the maleic anhydride ring (Formula 1wherein j is greater than zero) is opened by a base hydrolysis beforeuse as the stain resist. Preferably, the anhydride ring is opened afterthe alkoxy (for instance acetoxy) group has been removed. Hydrolysis ofthe polymer of Formula 2 yields the polymer of Formula 1.

The sulfonation of the hydoxystyrene moieties in the polymers of Formula1 is also accomplished by means known to those skilled in the art. Forinstance, sulfonation can be achieved by treatment of the polymer withsulfuric acid of various concentrations, by the use of fuming sulfuricacid, and most readily by the use of sulfur trioxide or its complexes,including the dimethylformamide complex or the dioxane complex.Sulfonation occurs on the hydroxystyrene residue, predominantly ortho tothe hydroxy group for p-hydroxystyrene or ortho or para to the hydroxygroup for other hydroxystyrene isomers. When styrene monomer is presentin the polymer, sulfonation occurs preferentially on the hydroxystyrenemonomer moiety.

The term “degree of sulfonation”, represented by m in Formula 1, is usedto describe the average number of sulfonic acid groups perhydroxystyrene residue. A degree of sulfonation of zero is theunsulfonated polymer, a degree of sulfonation greater than zero to lessthan 1.0 denotes an average of less than one sulfonic acid group perhydroxystyrene residue. For steric reasons there will be a degree ofrandomness in the sulfonation along the polymer chain. The degree ofsulfonation for Formula 1 is from about 0.01 to about 0.5 and preferablyabout 0.01 to about 0.4.

Sulfonation adds a strongly acidic group to the polymer which isexpected to exist in an anionic state under conditions relevant toapplication of stain blockers to substrates. This renders unoccupied dyesites in the treated substrate less available to potential staining.Sulfonation also increases the water solubility of the polymers andhydrolyzed polymers, an important factor in their application asstainblockers.

The sulfonated polymer of Formula 1 is isolated. For example, byremoving the dimethylformamide solvent and then precipitating in anon-solvent such as diethyl ether or hexane. The solid polymer thusobtained can be re-dissolved in a solvent such as methanol andoptionally reprecipitated to remove impurities. The polymer is thenredissolved or dispersed in water at a concentration of from about 15%to about 30% by weight solids to provide a formulation for treatment ofsubstrates. The aqueous solutions are adjusted to a neutral pH range ofabout 6 to about 7.

Unsulfonated polymers are also useful in the present invention toprovide stain resistance to substrates. These are included in Formula 1Abelow.

wherein

R¹, R², R³, R⁴, R⁷, M, h, i, j, k, and n are defined as in Formula 1 andp is 0 to about 0.5. Formula 1A is the same structure as Formula 1except that p is 0 to about 0.5, and preferably 0 to about 0.4.Unsulfonated polymers of Formula 1A are prepared and isolated asdescribed above for the sulfonated polymers except that the sulfonationstep is omitted when p is zero. For polymers of Formula 1A, p representsthe degree of sulfonation as described above for m of Formula 1.

In a further embodiment, the present invention comprises the use ofaqueous solutions or dispersions of (a) polymers of Formula 1, (b)polymers of Formula 1A, or (c) mixtures thereof as stain resist agentsfor substrates. The invention comprises a method of treating substratesto provide stain resistance comprising contacting the substrate with atleast one polymer of the structure of Formula 1 or Formula 1 A asdescribed above, or mixtures thereof.

The dispersions or solutions of the polymers of Formula 1, Formula 1A,or mixtures thereof, are applied conventionally to the substrate, dried,and cured. Application methods include spray, foam flex-nip, pad,kiss-roll, beck, skein, and winch, brush, roll, spray, and immersion,each method optionally with heat and with humidity in the range of dryto saturated steam (100% relative humidity). In alternative embodimentsof the present invention, spray, foam, flex-nip, nip (dip and squeeze),liquid injection, overflow flood, and other application methods wellknown to those skilled in the art, are suitable for use forsimultaneous, tandem or sequential application of the stain resistpolymers of the present invention and other surface effect agents. Forinstance, a low wet pickup bath system can be interchanged with a lowwet pickup spray or foam system, and a high wet pickup bath system canbe interchanged with other high wet pickup systems, e.g., flex-nipsystem, foam, pad, or flood. The method employed determines theappropriate wet pickup and whether the application is made from one sideof the substrate (spray and foam applications) or both sides (flex-nipand pad).

The following Table provides typical parameters for some applicationmethods for the compositions of the present invention. TABLE 1 PreferredWet Pickup Wet Pickup Application Range (%) Range (%) Flex-nip 150-350200-300 Flood 100-500 200-300 Foam  20-200  50-150 Pad 100-500 200-300Spray  20-200  50-150

Many variations of the conditions for spray, foam, flex-nip, flood, andpad applications are known to those skilled in the art and suchvariations are suitable for use herein. In one preferred method forcarpet substrates the application is by exhaution at a wet pickup of500% at a concentration of polymer of from about 0.5% to about 3% activeingredient on weight of fiber (owf), preferably from about 1 to about 2%active ingredient owf. The percent active ingredient owf is equal to thewet pickup multiplied by (percent solids of polymer times amount ofpolymer in g divided by weight of application bath).

Other treatment aids that are known to those skilled in the art may beadded to the solutions or dispersions of polymers of the structure ofFormula 1, Formula 1A, or mixtures thereof, including additionalcomponents such as treating agents or finishes to achieve additionalsurface effects, or additives commonly used with such agents orfinishes. Such additional components comprise compounds or compositionsthat provide surface effects such as no iron, easy to iron, shrinkagecontrol, wrinkle free, permanent press, moisture control, softness,strength, anti-slip, anti-static, anti-snag, anti-pill, stainrepellency, stain release, soil repellency, soil release, waterrepellency, oil repellency, odor control, antimicrobial, sun protection,and similar effects. One or more such treating agents or finishes can becombined with the aqueous solution or dispersion of Formula 1 or 1A andapplied to the fibrous substrate. Other additives commonly used withsuch treating agents or finishes may also be present such assurfactants, blocked isocyanates, pH adjusters, cross linkers, wettingagents, hydrocarbon extenders, wax extenders, and other additives knownby those skilled in the art. Suitable surfactants include anionic,cationic, and nonionic. Preferred is an anionic surfactant such assodium lauryl sulfonate, available as DUPONOL WAQE from WitcoCorporation, Greenwich, Conn.

In a further embodiment, the present invention comprises substratestreated with at least one composition of Formula 1, or at least onecomposition of Formula 1 A, or mixtures thereof. Substrates suitable foruse in the present invention comprise fibrous substrates and includefibers, yarns, fabrics, textiles, nonwovens, carpets, leather, or paper.The fibrous substrates are made with natural fibers such as wool,cotton, jute, sisal, sea grass, paper, coir and cellulose, or mixturesthereof; or are made with synthetic fibers such as polyamides,polyesters, polyolefins, polyaramids, acrylics and blends thereof; orblends of at least one natural fiber and at least one synthetic fiber.By “fabrics” is meant natural or synthetic fabrics, or blends thereof,composed of fibers such as cotton, rayon, silk, wool, polyester,polypropylene, polyolefins, nylon, and aramids such as “NOMEX” and“KEVLAR.” By “fabric blends” is meant fabric made of two or more typesof fibers. Typically these blends are a combination of at least onenatural fiber and at least one synthetic fiber, but also can be a blendof two or more natural fibers or of two or more synthetic fibers.

The substrates are treated with the polymer of Formula 1 or Formula 1Aor mixtures thereof as described above. Preferably, the substrates aretreated in accordance with the method of the present invention describedabove.

Substrates so treated were superior to current commercial products inblocking coffee and mustard stains, while many retained stain resistanceto red dyes such as KOOL-AID, wash fastness and lightfastness. Thesuperior stain resistance of the polymers and treated substrates of thepresent invention provide several advantages. For example, the superiorresistance to coffee and mustard stains is advantageous in use of thetreated substrates in fabrics and textiles used in garments, homefurnishings, carpets, and other consumer products. The durability of thestain resistance when subjected to washing or UV light results insuperior performance over time.

MATERIALS AND TEST METHODS

The following materials and test methods were employed in the Examplesherein.

Sulfur trioxide N,N-dimethylformamide complex (SO₃.DMF), is availablefrom Aldrich Chemical, Milwaukee Wis.

Poly(p-hydroxystyrene), poly(p-hydroxystyrene-co-t-butylacrylate)(61:39), poly(p-hydroxystyrene-co-t-butylacrylate) (61:39), andpoly(p-hydroxystyrene) branched are all available from Du PontElectronic Polymers, LLP, Corpus Christi Tex.

Comparative Example A is a commercially available stain blockercomposition which is an aqueous dispersion of an olefin/maleic acidpolymer with phenol-formaldehyde resin and surfactant, obtained from E.I. du Pont de Nemours and Company, Inc., Wilmington Del.

The carpet material is a residential cut pile two ply 1150, 3.5 turnsper square inch (1.4 turns/cm), 5/32 gauge, pile height 0.5 inch (2.5cm), 30 oz. per square yard (1.2 kg/m³), dyed light blue and availablefrom Invista, Wilmington, Del.

Test Method 1—Application of Stain Resist onto Residential Carpet withExhaust in a Microwave Oven

Dyed and unbacked residential carpet (with various colors, styles, andfiber types) were cut into approximately 4 inch×4 inch squares(approximately 10 cm×10 cm) and each square weighed as dry carpetsamples. The weight was typically about 13 g. Each carpet sample wassaturated with water and then most of the water in the carpet wasremoved by mechanical means (such as by spin-drying or vacuumextraction) until the weight of water remaining in the carpeting wasabout 40% of the dry carpet weight.

The stain blocker application solutions were diluted to 2% activeingredient on weight of fiber (owf) (2% of the total water bath byweight). Surfactant, DOWFAX 2A4 (1 to 2 g), was added to the solution,and the solution was adjusted to pH 2 with sodium bisulfate. Thesolution was applied to the carpet at 500% wet pick up. The weight ofcarpet sample (grams) ×500% =grams of stain blocker solution applied.The stain blocker application solution was applied evenly to the wettedcarpet samples in an amount equal to 500% of the dry carpet sample (500%wet pickup), and manually worked into the substrate until the substratewas fully saturated.

A single layer of one or more of the treated carpet samples was placedon the bottom of a microwave-safe plastic tray (any microwaveableplastic tray of adequate size may be used) with the pile side up. A fewholes were punctured in the lid to prevent steam buildup, and the lidwas placed on the plastic tray.

Using a household microwave oven with a temperature probe (such as aGeneral Electric model JVM1660, from General Electric, SchenectadyN.Y.), the carpet was heated in the plastic tray at full power leveluntil the temperature reached between 195+/−2° F. (91+/−1° C.) and thetemperature held at that temperature for 2 minutes. The microwave oventemperature probe was used to control the temperature. The samples werethen rinsed thoroughly with water.

Most of the water in the carpet sample was removed by spin-drying withan extractor until the weight of water remaining in the carpeting wasabout 20 to 40% of the dry carpet weight. The carpet sample was thencompletely dried in an oven at between 160° F. and 180° F. (70° C. and80° C.); typically for about 25 to 35 minutes. The carpet samples wereallowed to cool completely, for at least 10-15 minutes, and to reachequilibrium with the room environment before proceeding with staintesting.

Although 2% active ingrediant owf was used in the Examples, it issuitable in the present invention to use a broader range of valuescalculated as follows:% active ingredient on weight of the fiber (% AI owf)=[(% Solids inStain Blocker×amount (g))/water bath total (g)]×wet pick up

The quantities of the stainblocker suitable for application to thecarpet substrate are the amounts as calculated to achieve the 500% wetpick up. In the present invention, these amounts can range from about0.5% to about 3% AI owf based on the weight of the substrate carpetsample, preferably from about 1 to about 2% AI owf.

Test Method 2—Coffee Stain Test

Carpet samples, 6.76×6.76-inch (17.2×17.2 cm) squares of dyed carpet,were cut and placed pile side up on a non-absorbent surface. The pilewas cleaned of any unattached materials by vacuuming. ORIGINAL MAXWELLHOUSE ground coffee (33.8 g), available from Maxwell House Coffee Co.,Tarrytown N.Y. was placed into a standard 10-cup coffee filter.Deionized water (1266.2 g) was added and the coffee brewed according tothe manufacturers' directions. The pH of the coffee was adjusted to 5.0using aqueous solutions containing either 30% aqueous sodium hydrogensulfate or 10% sodium hydroxide as needed. The coffee was poured into asuitable volumetric dispenser, capable of dispensing 50 mL portions andthe dispenser placed in the hot water bath at 62° C. The coffee wasallowed to come to a temperature 140° F. +/−5° F. (60° +/−2.8° C.) andremain at that temperature for 30+/−5 minutes prior to staining. A ring,in the shape of an open-ended cylinder was used, having a diameter ofthe smaller opening of 2.75 inch (7 cm). Such a ring is described for adifferent purpose in AATCC Test Method 175. The ring was placed at thecenter of the carpet sample, with the smaller diameter opening againstthe pile. The coffee dispenser was set to measure 50 mL, and purged onceprior to staining. With the ring pressed down into the pile, 50 mL ofcoffee was transferred into a container and immediately poured into thering and onto the carpet. The coffee was worked into the carpet evenlyand thoroughly with the base of the cup. The coffee was allowed to stainthe carpet for 4 hours +/−20 minutes. Then the carpet samples werethoroughly rinsed in cold water for at least 10 minutes until the rinsewater was clear. The carpet samples were extracted using vacuum andair-dried for 24 hours on a non-absorbent surface. The coffee stainsobtained by this procedure were rated using a delta E color differencemeasurement.

For color measurement with delta E color difference, the color of eachcontrol and test carpet was measured both before and after the coffeestain test.

The initial color of the carpet (L*, a*, b*) was measured on anunstained piece of carpet. The delta E is the difference between thecolor of the unstained and stained samples, expressed as a positivenumber. The color difference was measured using a Minolta Chroma MeterCR-410. Color readings were taken on several areas on the carpet sample,and the average delta E was reported. Control carpets were of the samecolor and construction as the carpets for test items. A delta E readingof zero represents no color difference between two samples. A largerdelta E value indicates a color difference between two samples. Colormeasurement with delta E is discussed in AATCC Evaluation Procedure 7“Instrumental Assessment of the Change in Color of a Test Specimen”.

The calorimetric delta E values from the coffee stain resist test on asample and control was used to calculate the “Percent Coffee Blocked”.The percent blocking of the stain is calculated as:

100(Delta E_(untreated)−Delta E_(treated))/Delta E_(untreated). Highervalues denote better stain blocking.

Test Method 3—Mustard Stain Test

A 2 inch (5.1 cm) brass ring is placed in the center of a 4 to 6 inch(10.2 to 15.2 cm) square sample of carpet placed on a non-absorbentsurface. For the mustard stain test, fifteen grams of French's yellowmustard available from Reckitt Benckiser, Inc., Wayne, N.J., were usedto create a stain by placing the mustard in the middle of the brass ringon the carpet, and then spreading and pressing the stain into the carpetsurface. After setting for 24 h, the excess mustard was (a) scraped off,(b) thoroughly rinsed with water, (c) extracted using vacuum, and (d)air-dried for 24 hours on a non-absorbent surface. The mustard stainsobtained by this procedure were rated using a visual stain rating scale(AATCC Red 40 Stain Scale) from AATCC Test Method 175. A visual ratingof 10 (complete stain removal) to 1 (maximum or unchanged stain) wasused that approximated the AATCC Red 40 Stain Scale (Test Method #175)with the mustard stains having the same discoloration as the numberedcolored film. The mustard stain was yellow while the discoloration ofthe AATCC Red 40 Stain Scale was red. Higher values indicate greatermustard stain resistance.

Test Method 4—Stain Test with Cherry Flavored KOOL-AID (24 h KA)

Cherry KOOL-AID stain testing was conducted on carpet samples 15 cm by15 cm. Acid dye stain resistance was evaluated using a procedure basedon the American Association of Textile Chemists and Colorists (AATCC)Method 175, “Stain Resistance: Pile Floor Coverings.” A stainingsolution was prepared by mixing 36.5 grams of sugar sweetened cherryKOOL-AID and 500 mL water. KOOL-AID is a trademark of Kraft GeneralFoods, Inc. The carpet sample to be tested was placed on a flatnon-absorbent surface and a hollow plastic cylinder having a 2-inch(5-cm) diameter was placed tightly over the carpet sample. Twenty mls.of KOOL-AID staining solution was poured into the cylinder and thesolution was allowed to absorb completely into the carpet sample. Thestain was worked into the carpet. The cylinder was then removed and thestained carpet sample was allowed to sit undisturbed for 24 h. Then thecarpets were rinsed thoroughly under cold tap water for at least 10minutes until the rinse water was clear. The carpet samples wereextracted using vacuum and air-dried for 24 hours on a non-absorbentsurface. The KOOL-AID stains obtained by this procedure were rated usinga visual stain rating scale (AATCC Red 40 Stain Scale) from AATCC TestMethod 175. A visual rating of 10 (complete stain removal) to 1 (maximumor unchanged stain) was obtained by using the AATCC Red 40 Stain Scale(Test Method #175) with the KOOL-AID stains having the samediscoloration as the numbered colored film. Higher values representsuperior stain resistance.

Test Method 5—UV Light Stability.

UV fastness was conducted according to the American Association ofTextile Chemists and Colorists (AATCC) Test Method 16. The Nylon carpetsamples were rated in accordance with the Grey Scale for color changeafter exposure to 40 AATCC AFU (adjusted fade units). A visual ratingranged from 5 (complete color fastness compared to an unexposed sample)to 1 (complete loss of color). A higher rating indicated superior UVlight stability.

Test Method 6—Shampoo Test or Wash Durability “WAQE KA”

The carpet sample was submerged for 5 minutes at room temperature in adetergent solution consisting of “DUPONOL WAQE”(300 g WAQE/18.92 L).“DUPONOL WAQE” is a 30-40% aqueous solution of sodium alkane sulfonates,available from Witco Corporation, Greenwich CT. The solution wasadjusted with 10% sodium phosphate to a pH of 9.8 to 10.2. The carpetsample was then removed, rinsed thoroughly under tap water, de-wateredby squeezing, extracted by spinning dry, and allowed to dry at ambienttemperature. The dry carpet sample was then tested and rated on a scaleof 1 to 10 according to Test Method 4. A higher value indicates superiorwash durability of the stain resist.

EXAMPLES Example 1

Into a 500-mL round-bottom flask was added poly(p-hydroxystyrene) (20 g,M.W. 11,200, Triquest LP) and dimethyl formamide (DMF, 160 mL). To theresulting solution was added sulfur trioxide N,N-dimethylformamidecomplex (SO₃.DMF, 12.7 g g, 83.33 mmol). The reaction mixture was heatedat 150° C. for 18 h in which time the solution went from yellow toamber. After cooling to room temperature the solvent was removed on arotary evaporator. The resulting oil was re-evaporated several timesfrom 50 mL methanol. The resulting oil was triturated with diethyl etheruntil a solid formed. The solid was collected by filtration and driedunder vacuum to yield solid 50% sulfonated poly(p-hydroxystyrene), 32.6g. Elemental analysis: C 54.78%, H 6.75%, N 5.71%, S 8.37%. A sample fortesting was prepared by adding the above solid (15 g) to deionized water(75 mL) and of 1N NaOH (14 mL). This solution was applied to carpetusing Test Method 1. The carpet was evaluated for stain resistance usingTest Methods 2 and 4. Test results are shown in Table 2.

Example 2

Into a 500-mL round-bottom flask was addedpoly(p-hydroxystyrene-t-butylacrylate) polymer (20 g, 61:39; DupontElectronic Polymers LLP, Lot No# 10020-51-FDP, see Materials) and DMF(120 mL). To the resulting solution was added SO₃.DMF (7.6 g) and theresulting solution heated at 150° C. with stirring for 18 h. Thereaction mixture was cooled to room temperature and the solvent removedin vacuo to give a brown oil. The oil was added to diethyl ether (200mL) and stirred for 30 min.; decanting the diethyl ether and repeatingthe procedure several times caused the polymer to solidify. The solidwas dried under high vacuum to give the product, 50% sulfonatedpoly(p-hydroxystyrene-acrylic acid) (61:39), 28.17 g. ¹H and ¹³C NMRshowed that the t-butyl group had been removed in the course of thesulfonation. Elemental analysis: C 53.66%, H 7.08%, N 6.53%, S 5.62%. Asample for stain blocker testing was prepared by dissolving the abovepolymer (15 g) in deionized water (50 mL) and 1N NaOH (9.5 mL). Thissolution was applied to carpet using Test Method 1. The carpet wasevaluated for stain resistance using Test Methods 2, 4, 5, and 6. Testresults are shown in Tables 2 and 3.

Example 3

Into a 500-mL round-bottom flask was addedpoly(p-hydroxystyrene-t-butylacrylate) polymer (20 g, 61:39; DupontElectronic Polymers LLP, Lot No. 10020-51-FDP, see Materials) and DMF(120 mL). To the resulting solution was added SO₃.DMF (3.8 g) and theresulting solution heated under nitrogen to 150° C. with stirring for 18h. The reaction mixture was cooled to room temperature and the solventremoved in vacuo to give a brown oil. The oil was added to diethyl ether(150 mL) and stirred for 30 min. Decanting the diethyl ether andrepeating the procedure several times caused the polymer to solidify.The solid was dried under high vacuum to give the product, 25%sulfonated poly(p-hydroxystyrene acrylic acid) (61:39), 26.48 g. ¹H and¹³C NMR showed that the t-butyl group had been removed in the course ofthe sulfonation. Elemental analysis: C 58.42%, H 7.47%, N 6.6%, S 3.09%.A sample for testing was prepared by dissolving the above polymer (15 g)in deionized water (60 mL) and adding 1 N NaOH (13 mL). This solutionwas applied to carpet using Test Method 1. The carpet was evaluated forstain resistance using Test Method 2. Test results are shown in Table 2.

Example 4

Into a 500-mL round-bottom flask was added poly(-p-hydroxystyrene) (20.0g, branched, Dupont Electronic Polymers LLP; Lot no: PB5-8007B; M.W.4934, see Materials) and DMF (80 mL). To the resulting orange solutionwas added SO₃.DMF (12.76 g). The reaction mixture was stirred and heatedat 150° C. under nitrogen atmosphere for 18 h. After cooling to roomtemperature, the solvent was removed in vacuo and the resulting thickoil stirred under diethyl ether (200 mL) for 30 min. The diethyl etherwas decanted off and the procedure repeated thrice to yield solid 50%sulfonated branched poly(p-hydroxystyrene), 35.5 g after drying in avacuum oven at 60° C. Elemental analysis: C 55.46%, H 6.66%, N 6.17%, S7.15%. A sample for stain blocker testing was prepared by dissolution ofthe above material (15.0 g) in deionized water (35 mL). This solutionwas applied to carpet using Test Method 1. The carpet was evaluated forstain resistance using Test Method 2. Test results are shown in Table 2.

Example 5

Into a 500-mL round-bottom flask was added poly(p-Hydroxystyrene) (20.0g, branched, Dupont Electronic Polymers LLP; Lot no: PB5-8007B; M.W.4934, see Materials) and DMF (75 mL). To the resulting orange solutionwas added SO₃.DMF (6.4 g). The reaction mixture was stirred and heatedat 150° C. under a nitrogen atmosphere for 18 h. After cooling to roomtemperature, the solvent was removed in vacuo and the resulting thickoil stirred under diethyl ether (200 mL) for 30 min. The diethyl etherwas decanted off and the procedure repeated thrice to give solid 25%sulfonated branched poly(p-hydroxystyrene), 32.8 g, after drying in avacuum oven at 60° C. Elemental analysis: C 60.92%, H 6.64%, N 5.44%, S4.42%. A sample for stain blocker testing was prepared by dissolution ofthe above material (15.0 g) in deionized water (35 mL). This solutionwas applied to carpet using Test Method 1. The carpet was evaluated forstain resistance using Test Method 2. Test results are shown in Table 2.

Example 6

To a solution of poly(p-hydroxystyrene-tert-butylacrylate ester) (61:39ratio, 25.0 g, 110.74 mmol; M.W 12,800; Lot No: 10020-51-FDP; fromDupont Electronic Polymers LLP, see Materials) in 1,4-dioxane (100 mL)was slowly added 2N hydrochloric acid (113.16 mL). The reaction mixturewas heated at reflux for 19 h. After cooling reaction mixture to roomtemperature, the solvent was removed under vacuum to obtain a solid. Tothe solid was slurried with 250 mL water and transferred to a glassfrit. The mixture was filtered and the collected solids were washed 3times with 150 mL water to remove residual acid. The solids were driedin a vacuum oven at 50° C. overnight to give unsulfonated PHS acrylicacid polymer (21.36 g). ¹H and ¹³C NMR showed removal of the t-butylgroups. A sample for testing was prepared by dissolving the abovematerial (15 g) in deionized water (75 mL) and 1N NaOH (28 mL). Thissolution was applied to carpet using Test Method 1. The carpet wasevaluated for stain resistance using Test Methods 2 and 4. Test resultsare shown in Table 2.

Example 7

Into a 500-mL round bottom flask was addedpoly-p-hydroxystyrene-t-butylacrylate (20 g, 61:39 monomer ratio byweight, from Dupont Electronic Polymers LLP, Lot No. 10020-51-FDP, seeMaterials) and DMF (120 mL). To the resulting solution was added,portion wise, DMF.SO3 (1.52 g) and the resulting solution heated to 150°C. with stirring for 18 h. The reaction mixture was cooled to roomtemperature and the solvent removed in vacuo at 100° C. to give a brownfoamy oil. The oil was added to diethylether (200 mL) and stirred for 30min. Decanting the ether and repeating the procedure repeatedly until issolidified. The solid was dried under high vacuum to give 10% sulfonatedpoly-p-hydroxystyrene acrylic acid (61:39), 22.5 g. ¹H and ¹³C NMRshowed that the t-butyl group had been removed in the course of thesulfonation. Elemental analysis: C 53.66%, H 7.08%, N 6.53%, S 5.62%. Asample for stain blocker testing was prepared by dissolving the abovepolymer (15 g) in deionized water (70 mL) and 2N NaOH (14 mL). Thissolution was applied to carpet using Test Method 1. The carpet wasevaluated for stain resistance using Test Method 2. Test results areshown in Table 2.

Example 8

Example 6 was repeated except tetrahydrofuran was employed instead of1,4-dioxane and the reaction mixture was refluxed for 20 hours. ¹H NMRshowed removal of the t-butyl group to yield unsulfonated PHS acrylicacid polymer. A sample for stain blocker testing was prepared bydissolving the above polymer (15 g) in deionized water (70 mL) and 2NNaOH (14 mL). This solution was applied to carpet using Test Method 1.The carpet was evaluated for stain resistance using Test Methods 2, 3,4, 5, and 6. Test results are shown in Tables 2,3and4.

Example 9

A solution of poly(p-hydroxystyrene-styrene-tert-butylacrylateester)(60:20:20 ratio)(30.0 g, 0.250 mmol; DuPont Electronic MaterialsLLP, Lot No: TA4-6041B) in tetrahydrofuran(150 g), concentratedhydrochloric acid (9 g), and water (16 g) was refluxed for 20 hours. Thesolution was cooled and evaporated to dryness. The solid was washed with3-100 ml portions of water and dried in a vacuum oven at 80° C. to yieldunsulfonated PHS-styrene-acrylic acid polymer. 1H NMR showed removal ofthe t-butyl group. A sample for stain blocker testing was prepared bydissolving the above polymer (23 g) in deionized water (100 mL) and 10%NaOH (23 mL) to give a solution with 18.8% solids.

This solution was applied to carpet using Test method 1. The carpet wasevaluated for stain resistance using test Methods 2, 3, 4, 5, and 6.Test results are shown in Tables 2,3 and 4.

Example 10

Into a 250-mL round bottomed flask was addedpoly(-hydroxystyrene-t-butylacrylate) (31 g, , 60:40 monomer ratio byweight, from Dupont Electronic Technologies LLP, see Materials) andDMF(80 g). The solution was heated to 100° C. and purged subsurface withnitrogen for 0.5 hours. Then a DMF-SO₃(11.5 g) slurry in DMF(20 g) wasadded over a 20 minute period. The solution was heated for 10 hours at100° C. The solution was then cooled and the DMF removed in vacuo. Thegreen oil was then washed with water(3-100 mL portions) to give 19.5 gof 8% sulfonated(poly-p-hydroxystyrene-acrylic acid). Elementalanalysis: C 66.3%1, H 6.99%, N 1.21%, S, 1.10%. A sample for stainblocker testing was prepared by dispersing 10.0 g of the above polymerin deionized water(60 g) and 10% sodium hydroxide(10.0 g) and heatingfor one hour at 70° C. to give a 16.0 wt % solution. This solution wasapplied to carpet using Test Method 1. The carpet was evaluated forstain resistance using Test Methods 2, 4 and 6. Test results are shownin Tables 2 and 4.

Example 11

Into a 250-mL round-bottomed flask was addedpoly(-hydroxystyrene-t-butylacrylate (31 g, 60:40 monomer ratio byweight, from Dupont Electronic Technologies LLP, see Materials) and DMF(90 g). The solution was heated to 100° C. and purged subsurface withnitrogen for 0.5 hours. Then a DMF-SO₃(5.8 g) slurry in DMF (10 g) wasadded over a 20-minute period. The solution was heated for 20 hours at100° C. The solution was then cooled and the DMF removed in vacuo. Thegreen oil was then washed with water (3-100 mL portions) to give 23.7 gof 15% sulfonated(poly-p-hydroxystyrene-acrylic acid). Elementalanalysis: C 62.5%1, H 6.65%, N 1.62%, S, 2.60%. A sample for stainblocker testing was prepared by dispersing 10.0 g of the above polymerin deionized water (60 g) and 10% sodium hydroxide(10.0 g) and heatingfor one hour at 70° C. to give a 16.6 wt % solution. This solution wasapplied to carpet using Test Method 1. The carpet was evaluated forstain resistance using Test Methods 2, 3, 4 and 6. Test results areshown in Tables 2 and 4.

Example 12

Into a 250 mL round-bottomed flask was added poly(p-hydroxystyrene (20g, from DuPont Electronic Polymers LLC) and dioxane(120 g). The solutionwas heated to 40° C. and stirred until the polymer was dissolved insolution. The DMF.SO₃(24.5 g) complex was added over a 30-minute period.The temperature was increased to 85° C. and it was stirred for 24 hours.A dark brown oil precipitated. The solution was decanted off and the oilwas washed with acetone(3-100 mL portions). The polymer was dried in anoven at 60° C. in vacuo. Elemental Analysis: S 7.25% best fits a 50%sulfonated poly(p-hydroxystyrene). A sample for stain blocker testingwas prepared by dissolving the above polymer (20.0 g) in deionized water(150 mL) and 10% NaOH (20 mL) to give a solution of 11.0% solids. Thissolution was applied to carpet using Test Method 1. The carpet wasevaluated for stain resistance using Test Methods 2, 3, 4, and 6. Testresults are shown in Tables 2 and 4.

Example 13

Into a 250-mL round-bottom flask was added poly(p-hydroxystyrene) (20 g,M.W. 8,000, Aldrich) and dimethyl formamide (DMF, 100 mL). To theresulting solution was added SO₃.DMF(7.6 g). The reaction mixture washeated at 120° C. for 10 hours. After cooling to room temperature thesolvent was removed on a rotary evaporator and then dried at 80° C. invacuo to yield solid 31% sulfonated poly(p-hydroxystyrene), 31.0 g.Elemental analysis: S 4.77%. A sample for testing was prepared by addingthe above solid (31 g) to deionized water (250 mL) and of 10% NaOH (12mL) to give a solution with 11.1 wt % solids. This solution was appliedto carpet using Test Method 1. The carpet was evaluated for stainresistance using Test Methods 2, 3, 4, and 6. Test results are shown inTables 2 and 4.

Example 14

Example 13 was repeated to yield 32% sulfonated poly(p-hydroxystyrene)29.2 g. Elemental analysis: S 4.91%. A sample for stain blocker testingwas prepared by dissolving the above polymer (10 g) in deionized water(50 mL) and 10% NaOH (8 mL). This solution was applied to carpet usingTest Method 1. The carpet was evaluated for stain resistance using TestMethods 2, 4 and 6. Test results are shown in Table 2.

Example 15

Into a 1-L round-bottomed flask was addedpoly(-hydroxystyrene-t-butylacrylate) (100.0 g, 60:40 monomer ratio byweight, from Dupont Electronic Technologies LLP, see Materials) andDMF(250 g). The solution was purged subsurface with nitrogen for 0.5hours at room temperature. Then a DMF-SO₃(30.6 g) slurry in DMF (30 g)was added over a 20-minute period. The solution was heated for 20 hoursat 150° C. The solution was then cooled and the DMF removed in vacuo.The green oil was then washed with water (3-100 mL portions) to give 103g of beige powder of 23% sulfonated(poly-p-hydroxystyrene-acrylic acid).Elemental analysis: C 55.63%, H 6.86%, N 3.81%, S 3.21%. A sample forstain blocker testing was prepared by dissolving the above polymer (75g) in deionized water (250 mL) and 10% NaOH (75 mL) to give a solutionwith 19.4% solids. This solution was applied to carpet using TestMethod 1. The carpet was evaluated for stain resistance using TestMethods 2, 3, 4, 5, and 6. Test results are shown in Tables 2, 3 and 4.

Example 16

Into a 250-mL round-bottomed flask was addedpoly(-hydroxystyrene-styrene-t-butylacrylate) (30 g, 60:20:20 monomerratio by weight, from Dupont Electronic Technologies LLP, see Materials)and DMF (100 g). The solution was purged subsurface with nitrogen for0.5 hours at room temperature. Then a DMF-SO₃(6.9 g) slurry in DMF (30g) was added over a 20-minute period. The solution was heated for 20hours at 150° C. The solution was then cooled and the DMF removed invacuo. The orange oil was then washed with water (3-100 mL portions) togive 30.4 g of 18% sulfonated(poly-(p-hydroxystyrene-styrene-acrylicacid). Elemental analysis: C 69.5%1, H 7.18%, N 2.39%, S, 2.49%. Asample for stain blocker testing was prepared by dispersing 20.0 g ofthe above polymer in deionized water (90 g) and 10% sodiumhydroxide(20.0 g) and heating for one hour at 70C to give a 19.3 wt %solution. This solution was applied to carpet using Test Method 1. Thecarpet was evaluated for stain resistance using Test Methods 2, 3, 4, 5,and 6. Test results are shown in Tables 2, 3 and 4.

Example 17

Into a 1-L round-bottomed flask was addedpoly(-hydroxystyrene-t-butylacrylate) (93.0 g, 60:40 monomer ratio byweight, from Dupont Electronic Technologies LLP, see Materials) andDMF(240 g). The solution was purged subsurface with nitrogen for 0.5hours at 100° C. Then a DMF-SO₃(34.5 g) slurry in DMF(60 g) was addedover a 15-minute period. The solution was heated for 20 hours at 100° C.The solution was then cooled and the DMF removed in vacuo. The green oilwas then washed with water(3-100 mL portions) to give 64 g of beigepowder of 25% sulfonated(poly-p-hydroxystyrene-acrylic acid). Elementalanalysis: C 59.73, H 7.34, N 4.33, S 3.27%. A sample for stain blockertesting was prepared by dissolving the above polymer (64 g) in deionizedwater (350 mL) and 10% NaOH (60 mL) and heating to 70° C. to give asolution with 13.5% solids. This solution was applied to carpet usingTest Method 1. The carpet was evaluated for stain resistance using TestMethod 2, 3, and 4. Test results are shown in Tables 2, 3 and 4.

Comparative Example A

Comparative Example A was diluted and applied to carpet using TestMethod 1 and tested using Test Methods 2, 3, 4, 5, and 6. Test resultsare shown in Tables 2, 3 and 4.

Comparable Example B

Into a 500-mL round-bottom flask was addedpoly(p-hydroxystyrene-t-butylacrylate) co-polymer (20 g, 61:39%, DupontElectronic Polymers LLP, Lot No. 10020-51-FDP, see Materials) and DMF(120 mL). To the resulting solution was added SO₃.DMF (15.19 g) and theresulting solution was heated at 150° C. with stirring for 18 h. Thereaction mixture was cooled to room temperature and the solvent removedin vacuo to give a brown oil. The oil was added to diethyl ether (200mL) and stirred for 30 min.; decanting the diethyl ether and repeatingthe procedure several times caused the polymer to solidify. The solidwas dried under high vacuum to give the product, 100% sulfonatedpoly(p-hydroxystyrene-acrylic acid) (61:39), 36.7 g. ¹H and ¹³C NMRshowed that the t-butyl group had been removed in the course of thesulfonation. Elemental analysis: C 48.69%, H 6.0%, N 7.15%, S 8.29%. Asample for stain blocker testing was prepared by dissolving the abovepolymer (15 g) in deionized water (45 mL) and 1N NaOH (8.5 mL). Thissolution was applied to carpet using Test Method 1. The carpet wasevaluated for stain resistance using Test Method 2. Test results areshown in Table 2.

Comparative Example C

Into a 500-mL round-bottom flask was added poly(p-hydroxystyrene) (20.0g, branched, Dupont Electronic Polymers LLP; Lot no: PB5-8007B; M.W.4934, see Materials) and DMF (110 mL). To the resulting orange solutionwas added SO₃.DMF (25.53 g). The reaction mixture was stirred and heatedat 150° C. under nitrogen atmosphere for 18h. After cooling to roomtemperature, the solvent was removed in vacuo and the resulting thickoil stirred under diethyl ether (200 mL) for 30 min. The diethyl etherwas decanted off and the procedure repeated thrice to give solidproduct, 100% sulfonated branched poly(p-hydroxystyrene), 43.2 g, afterdrying in a vacuum oven at 60° C. Elemental analysis: C 47.34%, H 6.12%,N 7.44%, S 10.85%. A sample for stain blocker testing was prepared bydissolution of the above material (15.0 g) in deionized water (35 mL).This solution was applied to carpet using Test Method 1. The carpet wasevaluated for stain resistance using Test Method 2. Test results areshown in Table 2.

Comparative Example D

Into a 250 mL round-bottomed flask was added poly(p-hydroxystyrene (20g, from DuPont Electronic Polymers LLC) and dioxane(120 g). The solutionwas heated to 40° C. and stirred until the polymer was dissolved insolution. The DMF.SO₃(24.5 g) was added over a 30-minute period. Thetemperature was increased to 85° C. and it was stirred for 24 hours. Adark brown oil precipitated. The solution was decanted off and the oilwas washed with acetone(3-100 mL portions). The polymer was dried in anoven at 60° C. in vacuo to give an 86% sulfonated product. ElementalAnalysis: S, 14.95%. A sample for stain blocker testing was prepared bydissolving the above polymer (20.0 g) in deionized water (100 mL) and10% NaOH (42 mL) to give a solution of 19.8% solids. This solution wasapplied to carpet using Test Method 1. The carpet was evaluated forstain resistance using Test Methods 2, 4 and 6. Test results are shownin Tables 2 and 4.

Comparative Example E

Example 13 was repeated except twice the amount of DMF-SO3 adduct (15.0g) was employed, yielding 63% sulfonated poly(p-hydroxystyrene).Elemental analysis: S 9.58%. A sample for stain blocker testing wasprepared by dissolving the above polymer (43 g) in deionized water (150mL) and 10% NaOH (20 mL) to yield a 12.1 weight % solution. Thissolution was applied to carpet using Test Method 1. The carpet wasevaluated for stain resistance using Test Methods 2, 4, and 6. Testresults are shown in Table 2.

The following notes apply to Tables 2, 3, and 4

-   -   (a) Abbreviations:        -   PpHS=Poly(para-hydroxystyrene),        -   AA=acrylic acid, and        -   STYR=styrene, each as a monomer in a polymer.        -   Polymers are shown as PpHS(61)/AA(39)    -   (b) Test Method abbreviations:        -   24 h KA: Test Method 4        -   WAQE KA: Test Method 6        -   UV 40 AFU: Test Method 5        -   % Coffee Blocked: Test Method 2        -   % Mustard Blocked: Test Method 3    -   (a) NT means not tested.    -   (b) For all tests, higher values denote better performance.    -   (e) For % Coffee Blocked and % Mustard Blocked, a higher        percentage indicates superior performance.

(f) Different test sets are separated by heavy lines. Due to carpetsample variations, comparisons are made within test sets. TABLE 2 %Exam- 24 h WAQE Coffee ple Polymer (a) KA KA Blocked 1  50% sulfonatedPpHS 9.5 NT 28 6 PpHS(61)/AA(39) 10 NT 38 Comp. Commercialpolycarboxylate-based NT NT 40 Ex. A stain blocker A 4  50% sulfonatedbranched PpHS NT NT 38 5  25% sulfonated PpHS NT NT 37 Comp. Commercialpolycarboxylate-based NT NT 35 Ex. A stain blocker A Comp. 100%sulfonated NT NT 31 Ex. B PpHS(60)/AA(40) 2  50% sulfonatedPpHS(60)/AA(40) 10 7 37 Comp. Commercial polycarboxylate-based 9.5 6 19Ex. A stain blocker A 3  25% sulfonated PpHS(61)/AA(39) NT NT 25 7  10%sulfonated PpHS(61)/AA(39) NT NT 34 Comp. 100% sulfonated branched PpHSNT NT 15 Ex. C Comp. Commercial polycarboxylate-based NT NT 35 Ex. Astain blocker A 10   8% sulfonated PpHS(60)/AA(40) 10 9.5 33 11   15%sulfonated PpHS(60)/AA(40) 7 4 22 12   50% sulfonated PpHS 9 9 25 Comp.Commercial polycarboxylate-based 10 7 21 Ex. A stain blocker A Comp. 86% sulfonated PpHS 3 2 4 Ex. D 13   31% sulfonated PpHS(Aldrich) 9.5 933 Comp.  62% sulfonated PpHS(Aldrich) 9 6 26 Ex. E Comp. Commercialpolycarboxylate-based 9 7 29 Ex. A stain blocker A 14   32% sulfonatedPpHS 10 9.5 39 Comp. Commercial polycarboxylate-based 9 9 31 Ex. A stainblocker A 8 PpHS(60)/AA(40) 10 8 42 9 PpHS(60)/STYR(20)/AA(20) 6 5 51Comp. Commercial polycarboxylate-based 9 7 33 Ex. A stain blocker A 15  23% sulfonated PpHS(60)/AA(40) 10 9 36 16   18% sulfonated 10 9 41PpHS(60)/STYR(20)/AA(20) Comp Commercial polycarboxylate-based 9 8 24Ex. A stain blocker A 17   25% sulfonated PpHS 9.5 NT 26 Comp.Commercial polycarboxylate-based 9 NT 19 Ex A stain blocker A

TABLE 3 % 24 h WAQE UV 40 Coffee Example Polymer (a) KA KA AFU Blocked 250% sulfonated 10 7 4.5 37 PpHS(60)/AA(40) Comp. Commercial poly- 9.5 64 19 Ex. A carboxylate- based stain blocker A 8 PpHS(60)/AA(40) 10 8 342 9 PpHS(60)/STYR(20)/ 6 5 2.5 51 Comp. Commercial AA(20) 9 7 3.5 33Ex. A polycarboxylate- based stain blocker A 15  23% sulfonated 10 9 2.536 PpHS(60)/AA(40) 16  18% sulfonated 10 9 2.5 41 PpHS(60)/STYR(20)/AA(20) Comp Commercial poly- 9 8 3 24 Ex. A carboxylate- based stainblocker A

TABLE 4 Example Polymer (a) Mustard Stain 10  8% sulfonatedPpHS(60)/AA(40) 6 11 15% sulfonated PpHS(60)/AA(40) 7 12 50% sulfonatedPpHS 5 Comp. Ex. A Commercial polycarboxylate-based stain 2 blocker AComp. Ex. D 86% sulfonated PpHS 1 13 31% sulfonated PpHS(Aldrich) 4Comp. Ex. E 62% sulfonated PpHS(Aldrich) 2 Comp. Ex. A Commercialpolycarboxylate-based stain 2 blocker A  8 PpHS(60)/AA(40) 4  9PpHS(60)/STYR(20)/AA(20) 5 Comp. Ex. A Commercial polycarboxylate-basedstain 2 blocker A 15 23% sulfonated PpHS(60)/AA(40) 4 16 18% sulfonated3 PpHS(60)/STYR(20)/AA(20) Comp Ex. A Commercial polycarboxylate-basedstain 2 blocker A 17 25% sulfonated PpHS 5 Comp. Ex A Commercialpolycarboxylate-based stain 2 blocker A

The results in Tables 2 and 4 demonstrated that both the sulfonated andunsulfonated p-hydroxystyrene polymer stain resists of the presentinvention block coffee and mustard to a greater extent than a commercialpolycarboxylate stain resist (Comparative Example A). These examples ofthe present invention are also often comparable or better in durabilityand resistance to red dyes such as KOOL-AID, depending on the polymerand the extent of sulfonation. The less sulfonated polymers (<50%) ofthe present invention gave the best overall performance of blockingmustard and coffee. The heavily sulfonated Comparative Examples showedless desirable blocking with the coffee stain (Comparative Examples B,C, D, E), and with mustard stains (Comparative Examples D and E). Theunsulfonated polymers of Examples 6, 8 and 9 also showed superior coffeeand mustard blocking when compared to a commercial polycarboxylate(Comparative Example A). Example 8 also showed superior durability andresistance to staining with red dye (KOOL-AID) performance.

The data in Table 3 showed the sulfonated and unsulfonatedp-hydroxystyrene polymers of the present invention also demonstratedsuperior UV light stability by Test Method 5 when compared to commercialpolycarboxylate (Comparative Example A).

The results further demonstrated that the compositions of the presentinvention (see Example 2) have a better combination of properties.Example 2 was equal or to or better than Comparative Example A inresistance to red dye (KOOL-AID), durability, and light fastness, andmuch better in coffee stain blocking.

1. A composition comprising a polymer of Formula 1 having the followingrepeating units, said units occurring in any sequence

wherein R¹ is H, methyl or ethyl; R² and R³ are each independently H, C₁to about C₁₀ alkyl, —COOR⁴, CONR⁵R⁶, or —CN; R⁴ is M, C₁ to about C₂₀alkyl, or C₆ to C₁₀ aryl; R⁵ and R⁶ are each independently H, C₁ to C₁₀alkyl, C₆ to C₁₀ aryl, or R⁵ and R⁶ together with the nitrogen atom forma morpholine, pyrrolidine, or piperidine ring; R⁷ is a C₄ to C₈ alkylgroup; M is H, an alkali metal or alkali earth metal; h is about 10 to100 mole %; i is 0 to about 80 mole %; j is 0 to about 60 mole %; k andn are each independently 0 to about 40 mole %; and m is 0.01 to about0.5; provided that h+i+j+k+n equals 100, and provided that i+j+k+n isgreater than zero, except when h is 100%.
 2. The composition of claim 1wherein m is from about 0.05 to about 0.4
 3. The composition of claim 1wherein h is from about 40 to about 70 mole %.
 4. The composition ofclaim 1 wherein i is from about 30 to about 60 mole %.
 5. Thecomposition of claim 1 wherein j is from about 30 to about 60 mole %. 6.The composition of claim 1 wherein k and n are each independently fromabout 0 to about 10 mole %.
 7. The composition of claim 1 wherein themole % ratio of h to i is from about 50:50 to about 70:30.
 8. Thecomposition of claim 1 wherein the mole % ratio of h to i is about60:40.
 9. The composition of claim 1 wherein j, k, and n are each zero.10. The composition of claim 1 wherein R¹, R⁴, R⁵ and R⁶ are eachindependently H or methyl.
 11. The composition of claim 1 wherein R¹ isH or methyl, R² is H, R³ is —COOR⁴, and R⁴ is H or methyl.
 12. A methodof providing resistance to stains in substrates comprising contactingthe substrate with at least one polymer of Formula 1A having thefollowing repeating units, said units in any sequence

wherein R¹ is H, methyl or ethyl; R² and R³ are each independently H, C₁to about C₁₀ alkyl, —COOR⁴, CONR⁵R⁶, or —CN; R⁴ is M, C₁ to about C₂₀alkyl, or C₆ to C₁₀ aryl; R⁵ and R⁶ are each independently H, C₁ to C₁₀alkyl, C₆ to C₁₀ aryl, or R⁵ and R⁶ together with the nitrogen atom forma morpholine, pyrrolidine, or piperidine ring; R⁷ is a C₄ to C₈ alkylgroup; M is H, an alkali metal or alkaline earth metal; h is about 10 to100 mole %; i is 0 to about 80 mole %; j is 0 to about 60 mole %; k andn are each independently 0 to about 40 mole %; and p is 0 to about 0.5;provided that h+i+j+k+n equals 100, and provided that i+j+k+n is greaterthan zero, except when h is 100%.
 13. The method of claim 12 wherein mis from about 0.05 to about 0.4, h is from about 40 to about 70 mole %,i is from about 30 to about 60 mole %, j is from about 30 to about 60mole %, and k and n are each independently from about 0 to about 10 mole%.
 14. The method of claim 12 wherein the mole % ratio of h to i is fromabout 50:50 to about 70:30.
 15. The method of claim 12 wherein j, k, andn are each zero.
 16. The method of claim 12 wherein R¹ is H or methyl,R² is H, R³ is —COOR⁴, and R⁴ is H or methyl.
 17. The method of claim 12wherein the contacting is by means of spray, foam flex-nip, nip, pad,kiss-roll, beck, skein, winch, brush, roll, spray, immersion, liquidinjection, and overflow flood.
 18. The method of claim 12 wherein thepolymer is contacted with the substrate in an amount of from about 0.5%to about 3% active ingredient on weight of fiber.
 19. The method ofclaim 12 wherein the stain is coffee.
 20. The method of claim 12 whereinthe stain is mustard.
 21. A substrate treated in accordance with themethod of claim
 12. 22. A substrate which has been treated with at leastone polymer of Formula 1A having the following repeating units, saidunits in any sequence

wherein R¹ is H, methyl or ethyl; R² and R³ are each independently H, C₁to about C₁₀ alkyl, —COOR⁴, CONR⁵R⁶, or —CN; R⁴ is M, C₁ to about C₂₀alkyl, or C₆ to C₁₀ aryl; R⁵ and R⁶ are each independently H, C₁ to C₁₀alkyl, C₆ to C₁₀ aryl, or R⁵ and R⁶ together with the nitrogen atom forma morpholine, pyrrolidine, or piperidine ring; R⁷ is a C₄ to C₈ alkylgroup; M is H, an alkali metal or alkali earth metal; h is about 10 to100 mole %; i is 0 to about 80 mole %; j is 0 to about 60 mole %; k andn are each independently 0 to about 40 mole %; and p is 0to about 0.5;provided that h+i+j+k+n equals 100, and provided that i+j+k+n is greaterthan zero, except when h is 100%.
 23. The substrate of claim 22 which isa fiber, yarn, textile, fabric, carpet, leather or paper.
 24. Thesubstrate of claim 22 which is resistant to staining by coffee andmustard while maintaining light fastness and wash fastness.
 25. Acomposition comprising a polymer of Formula 2 having the followingrepeating units, said units occurring in any sequence

wherein R¹ is H, methyl or ethyl; R² and R³ are each independently H, C₁to about C₁₀ alkyl, —COOR⁴, CONR⁵R⁶, or —CN; R⁴ is H, C₁ to about C₂₀alkyl, or C₆ to C₁₀ aryl; R⁵ and R⁶ are each independently H, C₁ to C₁₀alkyl, C₆ to C₁₀ aryl, or R⁵ and R⁶ together with the nitrogen atom forma morpholine, pyrrolidine, or piperidine ring; R⁷ is a C₄ to C₈ alkylgroup; R8 is H, C₁ to about C₂₀ alkyl, or C₆ to C₁₀ aryl; R⁹ is H, R¹⁰,or C(O)R¹¹; R¹⁰ is C₁ to about C₄ alkyl; R¹¹ is C₁ to about C₄ alkyl, orC₆ to C₁₀ aryl; h is about 10 to 100 mole %; i is 0 to about 80 mole %;j is 0 to about 60 mole %; k and n are each independently 0 to about 40mole %; and m is 0.01 to about 0.5; provided that h+i+j+k+n equals 100,and provided that i+j+k+n is greater than zero, except when h is 100%.26. The composition of claim 25 wherein m is from about 0.05 to about0.4
 27. The composition of claim 25 wherein h is from about 40 to about70 mole %.
 28. The composition of claim 25 wherein i is from about 30 toabout 60 mole %.
 29. The composition of claim 25 wherein j is from about30 to about 60 mole %.
 30. The composition of claim 25 wherein k and nare each independently from about 0 to about 10 mole %.
 31. Thecomposition of claim 25 wherein the mole % ratio of h to i is from about50:50 to about 70:30.
 32. The composition of claim 25 wherein the mole %ratio of h to i is about 60:40.
 33. The composition of claim 25 whereinj, k, and n are each zero.
 34. The composition of claim 25 wherein R¹,R⁴, R⁵ and R⁶ are each independently H or methyl.
 35. The composition ofclaim 25 wherein R¹ is H or methyl, R² is H, R³ is —COOR⁴, and R⁴ is Hor methyl.